GIS SCIENCE JOURNAL ISSN NO : 1869-9391 REVIEW ON THE PRODUCTION OF BIOETHANOL FROM BIOMASS Liny.P™, Bhagyashroe Hosmani", Divyashree R’, Girish'and Sagar Vasudev Kesari! “Acharya Institute of Technology: Soladevanahalli, Bangalore-107, Karnataka, India Abstract: The increasing global demand for energy and advances in new biofuel production routes have increased the research on the potential of biofuels. Fasil fuels are a major contributor to climate change, ‘and as the demand for energy production increases, alternative sources (e.., renewables) are becoming more ‘attractive. Biofuels such as bioethanol reduce reliance on fossil fuels and can be compatible with the existing feet of internal combustion engines. The incorporation of biofuels can reduce internal combustion engine (ACE) fleet carbon diaxide emissions. Bioethanol is typically produced via microbial fermentation of fermentable sugars, such as glucose, fo ethanol. Traditional feedstocks (e.g, first-generation feedstock) include cereal grains, sugar cane, and sugar beets. However, due to concerns regarding food sustainability. lignocellulosic (second-generation) and algal biomass (third-generation) feedstocks have been investigated. Ethanol yield from fermentation is dependent on a multitude of factors. This review compares bioethanol production from « range of feedstocks und elaborates on avaiiable technologies, including fermentation practices. The importance of maintaining nutrient homeostasis of yeast is also examined. The purpose of this review is 10 provide insight info available technologies, yields of bioethanol achieved by current ‘manufacturing practices, and goals for future innovation, Keywords: Bioethanol, fossil fuels, energy, renewable sources, feedstocks 1. Introduction Energy requirements in near future depend on alternative renewable energy sources as there is an exhaustion of fossil fuels. Altemative renewable sources include wide sources of which biomass is one alternate source of energy used in the present scenario. For instance, biological degradation of lignocellulosic biomass feedstock to produce biofuels such as bioethanol, biodiesel, and biohydrogen. Biofuels are eco-friendly and sustainable sources of energy. It is used as fuel for engines and as an additive for fuel, recently biodiesel and bioethanol are used as a blend with petroleum-based fuels. Bioethanol production from lignocellulosic materials will be up to 442 billion liters/ year. For example, the rice straw of 731 million tons is distributed in Africa (20.9 million tons), Asia (667.6 million tons), Europe (3.9 million tons), America (37.2 million tons), and Oceania (1.7 million tons). It can potentially produce 205 billion liters of bioethanol per year [1,2] Bioethanol is most commonly blended with gasoline in concentrations of 10% bioethanol to 90% gasoline, known as E10 or “‘gasohol”, Bioethanol is used as a 5% blend with petrol under the European Union (EU) quality standard EN228. It does not require engine modification [3] Bioethanol is one of the promising biofuels. Large-scale manufacture of bioethanol as fuel is obtained from first-generation feedstock such as sugarcane, com, sweet sorghum, sugar beet, etc.,[4,5]. But this might lead to food scarcity problems. Hence, this review is focused on second and third-generation feedstock including crop residues and alga Algae as the primary source of third-generation feedstock used are the best option for the production of bioethanol. It is duc to its productivity, cultivation, andGIS SCIENCE JOURNAL ISSN NO : 1869-9391 convenient harvesting time [4-9]. They have high lipid content, and their cellulosic structure and carbohydrate content presence contribute to bioethanol production directly. Low contents of lignin in algae make enzymatic hydrolysis of seaweeds with little or no pre-treatment possible. Also, favorable net carbon dioxide emissions between the production of bioethanol, combustion, and carbon dioxide uptake during photosynthesis lead to carbon neutrality. Algae has higher photosynthetic efficiency of 6 to 8% compared to terrestrial biomass of 2%. Hence, they form sustainable feedstock for bioethanol production. Hence, bioethanol production from algae can overcome the problem of emission of greenhouse gases compared to fossil fuels. Also, algal production does not require agricultural lands and fertilizer for cultivation. Bioethanol has high octane number, which enables a high engine compression ratio leading to an increase in engine efficiency and performance. Bu, it has a low volumetric energy density, due to which a high volume is bioethanol is required compared to gasoline, 2. Pretreatment technologies for biomass Pre-treatment of the biomass is to obtain sugars directly or in the later stage by hydrolysis, to prevent the loss ot degradation of obtained sugats, limit the toxic materials that inhibit the production of ethanol, reduce the energy requirement, and minimize the cost of production. Methods of pre-treatments are namely., physical, chemical, physicochemical, and biological means [4]. Cost of the bioethanol production is based on the pre- ‘treatment process. But there is no specific best option for the technique, studies are carried out to improve the output and the cost of production [10] 2.1 Physical pre-treatments Mechanical comminution: It includes the techniques of chipping, grinding, and milling. It improves the efficacy of the process by decreasing the degree of polymerization and increasing the specific surface by decreasing the cellulose crystallinity. The energy that is required for the process depends on the initial and final structure of the particles, moisture content, and structure [4, 11]. Milling is preferred for the enzymatic hydrolysis of lignocellulosic materials. Pyrolysis: It is an endothermic process that requires less energy and biomass is, treated over the temperature of 300°C and degrades cellulose to char with the release of gaseous products like CO and Hy. Char will be washed with water or dilute acid, and the remaining content of the solution forms the carbon source to support microbial growth for bioethanol production. In the washing step, 50-55% of the biomass weight is reduced as 80- 85% of the cellulose will be converted into reducing sugars [4,12]. Microwave oven pre-treatment: It is a simple method, where reaction time is short but the heating efficiency is high with low energy input. The heat generated in biomass leads to vibration of a polar bond resulting in the explosion between the particles the lignocellulosic structure will be degraded. Pre-treatment effect of microwave rice straw and bagasse leads to the improvement in the production ofGIS SCIENCE JOURNAL ISSN NO : 1869-9391 total reduced sugar. Microwave pre-treatment is processed with chemical agents, for instance, alkaline reagents such as NasCOs, and Ca(OH): thus cellulose is, accessible to enzymes [13,14] 2.2, Physicochemical pre-treatments Steam explosion method: It is a technique in which biomass is heated under high-pressure steam (20-50 bar, 160-270 °C) for a few minutes, the process is continued until the atmospheric conditions are attained. Catalyst is not used in this, method, diffusion of steam into the matrix will help in the dispersion of fibers. Biomass such as wheat straw and sugarcane bagasse are subjected to this type of pre-treatment efficiently. On the degradation of biomass, levulinic acid, xylitol, and alcohols are obtained [15,16] Liquid hot water method: It is an environmental and economical method, it improves enzymatic hydrolysis. In this method, pressure is maintained to prevent evaporation and stabilize the water [17] Ammonia Fiber Explosion (AFEX): In this method, liquid ammonia and steam explosion are conducted simultaneously. Ammonia fiber explosion (AFEX) is a method that liquid ammonia and steam explosion are carried out together. In this, method, the biomass of 15-30% moisture content will be treated with liquid ammonia (1-2 kg NH /kg dry biomass). Maintaining the appropriate temperature pressure of 12 atm is essential. This method leads to the shredding of the biomass fibers, and decrystallization of cellulose, but is not effective on materials with high lignin content [15]. Enzymatic hydrolysis requires less amount of enzyme after AFEX. To enhance the process economically, ammonia will be recovered after pre-treatment. CO: explosion: It is carried out at a low temperature; hence the process is of low cost. There is no formation of inhibitors. Also, conversion yields are more [18] ‘Wet oxidation: It is the treatment of biomass with water and air or oxygen as a catalyst over the temperature of 120 °C. In this method, the solubility of hemicellulose and lignin are increased, but free hemicellulose molecules cannot be hydrolyzed. 2.3. Chemical pre-treatments It includes the treatment with dilute acid, alkaline, ammonia, organic solvent, and chemicals. Processes are simple and conversion yield is high in a short time [4] Acid pre-treatment: Acid is used as catalyst so that cellulose will be accessible to the enzymes. Acid pre-treatment can be carried out with concentrated acid or diluted acid The use of concentrated acid is less preferable, as it will lead to the formation of a high amount of inhibiting components [19]. Concentrated acids such as sulphuric acid, hydrochloric acid, nitric acid, and phosphoric acid are used. Dilute acids are applied at moderate temperatures to convert lignocellulosic structures to soluble sugars [15]. Biomass is pre-treated with dilute sulphuric acid at moderate temperature to hydrolyze hemicelluloses and facilitate enzymaticGIS SCIENCE JOURNAL ISSN NO : 1869-9391 hydrolysis leading to the formation of soluble sugars. In this process, biomass is hydrolyzed to hemicelluloses and then hydrolyzes to xylose and other sugar, further xylose is reduced to furfural, which is toxic in ethanol production. It will be recovered by distillation [15]. According to Miranda et al., (2012), acids with 2N lead to the highest sugar yield, but at a higher concentration from 2 to 10N, there will be a decrease in sugar yield [20]. Also, a study has indicated for the pre- treatment of softwood, a decrease in ethanol is noted with increasing acid concentration [20], Alkaline pre-treatment: It is carried out at low temperatures and pressure. In this, method, lignin is removed easily, but there is the formation of unrecoverable salts, also the solubility of hemicelluloses and cellulose is less [21]. Alkaline pre- treatment reduces the lignin and hemicellulose content of biomass and improves the surface area and helps water molecules for breaking bonds between hemicelluloses and lignin [15]. Catalysts used in this process include sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia [22]. The effects of alkaline pre-treatments depend on the type of biomass. [23, 24] Organosoly pre-treatment: In this method, organic solvents such as methanol, ethanol, acetone, and ethylene glycol are used along with the catalysts. Catalysts such as hydrochloric acid, sulphuric acid, sodium hydroxide, and ammonia are used in the process. In this process, pure and high-quality lignin is obtained as a by-product [25]. Removal of lignin improves the surface area and provides accessibility of enzymes to cellulose. Demerits of this process include oxidation, volatilization, and creating high risk in the process at high pressure. Other than that solvent must be recovered, or else it would lead to the formation of furfural and soluble phenols and reduce operation cost [26] 2.4, Biological pre-treatments This type of process is environmentally friendly, it requires less energy, the method is resistant to corrosion, and inhibitor formation is less [27]. Fungi will degrade lignin, hemicelluloses, and cellulose partially. But it requires a long process time, a large production area, and needs to control continuously for the growth of microorganisms [26]. Enzymatic hydrolysis is the step of hydrolysis of cellulose by specific cellulase enzymes. Obtained products after hydrolysis are reducing sugars that include glucose, Cost of the enzymatic hydrolysis is less than acid or alkaline hydrolysis as the reaction is carried out under mild conditions [50]. Cellulase enzymes obtained from bacteria and fungi are used in hydrolysi These microorganisms can be aerobic, anaerobic, mesophilic, or thermophilic. Enzyme and substrate-related factors affect enzymatic hydrolysis. 3.Characteristics of bioethanol The supernatant from enzymatic hydrolysis of lignocelluloses consists of six- carbon (hexoses) and five-earbon (pentoses) sugars if cellulose and hemicellulose are hydrolyzed. Depending on the lignocellulose source, the hydrolysate typically consists of glucose, xylose, arabinose, galactose, mannose, fucose, and rhamnose [28]GIS SCIENCE JOURNAL ISSN NO : 1869-9391 Microorganisms ean be used to treat lignocellulose-derived sugars into bioethanol. The efficiency of the process depends on compatibility with the existing product, processes, and equipment [29]. Factors considered for the process depend on fermentation time, temperature, pH, alcohol tolerance, growth rate, productivity, osmotic tolerance, specificity, yield, stability and tolerance towards inhibitors, carbon source concentration, nitrogen source, and inoculum size. Table 1, Properties of bioethanol S.No Properties Range 1 [MW 46.07 2] Octane number 108 3__| Density TO9kgim™ 4 Boiling point 78°C 35__| Freezing point 96.1 6 _| Flash point Ee 7 [Latent heat of vaporization RS4KIIKg Bioethanol has low energy content, therefore for applications in mobility, for a given tank volume, the range of the vehicle is reduced in the same proportion. The octane number of ethanol is higher than that for petrol, hence it has better antiknock characteristics. This property can be extensively analyzed if the compression ratio of the engine is adjusted accordingly. This in tum increases the fuel efficiency of the engine. The oxygen content of ethanol also leads to a higher efficiency, which results in a cleaner combustion process at relatively low temperatures. The Reid vapor pressure, a measure of the volatility of the fuel, is very low for ethanol. Thus, slow evaporation, which has the advantage that the concentration of evaporative emissions in the air remains relatively low, it will reduce the risk of explosions. However, the low vapor pressure of ethanol, together with its single boiling point, is disadvantageous with regard to engine start at low ambient temperatures. Below 200C, engines cannot be initiated with bioethanol. Hence it will be always used as a blend with gasoline or as an octane increaser with ethyl tertiary butyl ether (ETBE), consisting of 45 % per volume of bioethanol and 55 % per volume of isobutylene. Bioethanol is ixed with gasoline at the volume fractions of 5, 10, and 85 % (fuel names E5-E85). A total of 85 % bioethanol by volume can only be used in flexible fuel vehicles (FEV), while mixtures of 5 and 10 % by volume can be used without any engine modifications. However, problems related to the use of bioethanol are: the corrosive effect on fuel injectors and electric fuel pumps as bioethanol are hygroscopic in nature, engine start-up problems in cold weather conditions since pure ethanol is hard to vaporize, and the tribological effect on lubricant properties and engine performance. Bioethanol inside lubricant significantly reduces the properties and performance of engine oil. It is miscible with water but immiscible with oil. Therefore, bioethanol has a high potential for emulsion formation (bioethanol-water-oil mixture), which causes serious engine failures.GIS SCIENCE JOURNAL ISSN NO : 1869-9391 4. Applications ‘© Transport fuel to replace gasoline ‘© Fuel for power generation by thermal combustion ‘* Fuel for fuel cells by a thermochemical reaction ‘+ Fuel in co-generation systems ‘+ Feedstock in the chemical industry © Costeffective fuel as it is used as a blend with a small proportion of volatile fuel such as gasoline §.Conclusion ‘With the increase in the demand for energy globally, bioethanol produced from renewable value-added co-products feedstock is a valuable and eco-friendly alternative to non-renewable fuels. It can be an alternative solution in the current scenario and can be economically competitive over fossil fuels. In this aspect, bioethanol production from second and third-generation lignocellulosic nonedible biomass has gained interest. 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